Process for dyeing or printing hydroxyl group containing fibre materials

ABSTRACT

The invention relates to a process for dyeing or printing hydroxyl group containing fibre materials, which comprises using at least one yellow or orange dyeing dye of formula ##STR1## wherein the substituents are as defined in claim 1, together with at least one blue dyeing dye and/or at least one red dyeing dye. Level dyeings and prints with good allround fastness properties are obtained by the process of the invention.

The present invention relates to a process for dyeing or printinghydroxyl group containing fibre materials with dye mixtures by thedichromatic or trichromatic dyeing technique.

Dyeing or printing textile materials by the dichromatic or trichromatictechnique requires, inter alia, the use of dyes that have as level abuild-up as possible while at the same time having consistency of shadein different concentrations and good compatibility in order to obtaindyed or printed textile materials which substantially meet the demandsmade of them.

This object was not always achieved with the dyes and dye mixtures usedheretofore, especially with respect to compatibility, uptake, fibrelevelness and surface levelness, as well as allround fastness propertiessuch as wetfastness. Hence it is the object of this invention to provideimproved processes for dyeing and printing hydroxyl group containingfibre materials by the dichromatic or trichromatic dyeing technique.

It has now been found that the inventive process meets theaforementioned requirements.

Accordingly, the invention relates to a process for dyeing or printinghydroxyl group containing fibre materials, which comprises using atleast one yellow or orange dyeing dye of formula ##STR2## wherein R₁ andR₂ are hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen, carboxy, sulfo,ureido, unsubstituted C₂ -C₆ alkanoylamino or C₂ -C₆ alkanoylamino whichis substituted in the alkyl moiety, or unsubstituted or substitutedarylazo, R₃, R₄, R₅, R₆, R₇ and R₈ are hydrogen, C₁ -C₈ alkyl, C₁ -C₈alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety, and A₁ is a radical offormula ##STR3## wherein R and R' are hydrogen or unsubstituted orsubstituted C₁ -C₈ alkyl, Y₁ in the radical of formula (3) and Y₂ in theradical of formula (4) are hydroxy, C₁ -C₄ alkoxy, chloro, bromo, C₁ -C₄alkylthio, amino, N-mono- or N,N-di-C₁ -C₄ alkylamino which isunsubstituted or substituted in the alkyl moiety or moieties by hydroxy,sulfo, carboxy or C₁ -C₄ alkoxy, cyclohexylamino, phenylamino or N-C₁-C₄ alkyl-N-phenylamino which are unsubstituted or substituted in thephenyl moiety by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, carboxy, sulfo and/orhalogen, or are morpholino or 3-carboxy- or 3-carbamoylpyridin-1-yl, andB₁ in the radical of formula (4) is a linking group, together with atleast one blue dyeing and/or at last one red dyeing dye.

Halogen substituents R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ in formula (1)are each independently of one another fluoro, bromo or, preferably,chloro.

R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ in formula (1) and R and R' informulae (2) to (4) defined as C₁ -C₈ alkyl are typically methyl, ethyl,propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl,hexyl, heptyl and octyl. Preferably R₁, R₂, R₃, R₄, R₅, R₆, R₇, R₈, Rand R' are C₁ -C₄ alkyl.

The substituents R and R' in formulae (2) to (4) as C₁ -C₈ alkyl may besubstituted, conveniently by C₁ -C₄ alkoxy, C₁ -C₄ alkoxycarbonyl,hydroxy, halogen, typically chloro or fluoro, carboxy, cyano, sulfo orsulfato. Typical examples are carboxymethyl, β-carboxyethyl,methoxycarbonylmethyl, ethoxycarbonylmethyl, β-methoxyethyl,β-ethoxyethyl, β-chloroethyl, γ-chloropropyl, β-hydroxyethyl,β-hydroxybutyl, β-cyanoethyl, sulfomethyl, β-sulfoethyl, β-sulfatoethyl.

Preferably R and R' have the same meanings. R and R' are preferablyhydrogen or C₁ -C₄ alkyl, most preferably hydrogen.

R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ defined in formula (1) as C₁ -C₈alkoxy are preferably C₁ -C₄ alkoxy such as methoxy, ethoxy, propoxy,isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy.

R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ defined as C₂ -C₆ alkanoylamino informula (1) are preferably C₂ -C₄ alkanoylamino, typically acetylaminoor propionylamino. C₂ -C₆ Alkanoylamino as C₂ -C₆ alkanoylamino which issubstituted in the alkyl moiety is typically carboxy- or, preferably,hydroxy-substituted.

R₁ and R₂ as arylazo in formula (1) are each independently of the othertypically naphthylazo or, preferably, phenylazo radicals, each of whichradicals may be unsubstituted or further substituted by sulfo, C₁ -C₄alkyl, C₁ -C₄ alkoxy and/or halogen. Unsubstituted phenylazo orphenylazo which is substituted by sulfo, methyl, methoxy and/or chloroare preferred.

Typical examples of substituents Y₁ in formula (3) and Y₂ in formula (4)are hydroxy, methoxy, ethoxy, n- or isopropoxy, chloro, methylthio,ethylthio, amino, methylamino, ethylamino, carboxymethylamino,β-hydroxyethylamino, N,N-di-β-hydroxyethylamino, β-sulfoethylamino,phenylamino, o-, m- or p-methylphenylamino, o-, m- orp-methoxyphenylamino, o-, m- or p-chlorophenylamino, o-, m- orp-sulfophenylamino, 2,4- or 2,5-disulfophenylamino,o-carboxyphenylamino, N-ethyl-N-phenylamino, N-methyl-N-phenylamino andmorpholino.

Preferably Y₁ and Y₂ are each independently of the other chloro, amino,N-mono- or N,N-di-C₁ -C₄ alkylamino which are unsubstituted orsubstituted in the alkyl moiety or moieties by hydroxy, or arephenylamino or morpholino, preferably morpholino or chloro.

Suitable linking groups B₁ in formula (4) may conveniently be theradicals of formulae ##STR4## wherein R and R' have the aforementionedmeanings and preferred meanings. Preferably B₁ is a radical of formula(6).

It is preferred to use dyes of formula (1), wherein R₁, R₂, R₃, R₄, R₅,R₆, R₇ and R₈ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄alkanoylamino, halogen or sulfo. R₁, R₂, R₃ and R₄ are preferablyhydrogen or sulfo.

It is especially preferred to use dyes of formula (1), wherein R₁, R₂,R₃ and R₄ are hydrogen or sulfo, R₅, R₆, R₇ and R₈ are hydrogen, C₁ -C₄alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen or sulfo, B₁ is aradical of formula (6), and Y₁ and Y₂ are chloro, amino, N-mono- orN,N-di-C₁ -C₄ alkylamino which is unsubstituted or substituted in thealkyl moiety or moieties by hydroxy, or are phenylamino or morpholino,preferably morpholino or chloro.

It is most especially preferred to use as dyes of formula (1) dyes offormula ##STR5## wherein R₉ and R₁₀ are hydrogen, C₁ -C₄ alkyl, C₁ -C₄alkoxy, C₂ -C₄ alkanoylamino, halogen or sulfo, preferably hydrogen orC₂ -C₄ alkanoylamino, and A₂ is a radical of formula ##STR6## Dyesmeriting particular interest as dyes of formula (1) for the process ofthis invention are the dyes of formulae ##STR7## especially the dye offormula (11).

As blue dyeing dyes it is preferred to use in the inventive process atleast one dye of formulae (13), (14) and (15) ##STR8## wherein D₁ isunsubstituted or substituted phenyl or naphthyl, R₁₁, R₁₂, R₁₃ and R₁₄are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety and R₁₅ is hydrogen,unsubstituted or substituted C₁ -C₈ alkyl, C₂ -C₆ alkanoyl which isunsubstituted or substituted in the alkyl moiety, or phenyl or benzoylwhich are unsubstituted or substituted in the phenyl ring ##STR9##wherein D₂ and D₃ are unsubstituted or substituted naphthyl, and R₁₆ andR₁₇ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety, ##STR10## wherein R₁₈,R₁₉ and R₂₀ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl orC₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylaminowhich is unsubstituted or substituted in the alkyl moiety, and R₂₁ isunsubstituted or substituted C₁ -C₈ alkyl or phenyl.

Halogen substituents R₁₁, R₁₂, R₁₃ and R₁₄ in formula (13), R₁₆ and R₁₇in formula (14) and R₁₈, R₁₉ and R₂₀ in formula (15) are eachindependently of one another typically fluoro, bromo or, preferably,chloro.

R₁₁, R₁₂, R₁₃, R₁₄ and R₁₅ in formula (13), R₁₆ and R₁₇ in formula (14)and R₁₈, R₁₉, R₂₀ and R₂₁ in formula (15) defined as unsubstituted orsubstituted C₁ -C₈ alkyl are preferably C₁ -C₄ alkyl, typically methyl,ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl or isobutyl, aswell as the radicals substituted by e.g. C₁ -C₄ alkoxy, C₁ -C₄alkoxycarbonyl, hydroxy, halogen such as chloro or fluoro, carboxy,cyano, sulfo or sulfato.

R₁₁, R₁₂, R₁₃ and R₁₄ in formula (13), R₁₆ and R₁₇ in formula (14) andR₁₈, R₁₉ and R₂₀ in formula (15) defined as unsubstituted or substitutedC₁ -C₈ alkoxy are preferably C₁ -C₄ alkoxy, typically methoxy, ethoxy,propoxy, isopropoxy, butoxy, sec-butoxy, isobutoxy or tert-butoxy, aswell as the hydroxy- or carboxy-substituted radicals.

R₁₁, R₁₂, R₁₃ and R₁₄ in formula (13), R₁₆ and R₁₇ in formula (14) andR₁₈, R₁₉ and R₂₀ in formula (15) defined as C₂ -C₆ alkanoylamino arepreferably C₂ -C₄ alkanoylamino, typically acetylamino orpropionylamino. C₂ -C₆ Alkanoylamino which is substituted in the alkylmoiety may suitably by hydroxy-substituted.

R₁₅ as C₂ -C₆ alkanoyl in formula (13) is preferably C₂ -C₄ alkanoyl,typically acetyl or propionyl. C₂ -C₆ Alkanoyl which is substituted inthe alkyl moiety may suitably be hydroxy-substituted.

The substituents D₁ defined as phenyl or naphthyl, D₂ and D₃ asnaphthyl, R₁₅ as phenyl or benzoyl as well as R₂₁ as phenyl may beunsubstituted or substituted. Typical examples of substituents arehalogen, amino, sulfo, carboxy, ureido, C₂ -C₄ alkanoylamino which maybe further substituted in the alkyl moiety by hydroxy, C₁ -C₄ alkyl, C₁-C₄ alkoxy which may be further substituted by hydroxy or carboxy, aswell as benzoylamino or phenylamino which may be further substituted inthe phenyl ring by carboxy, halogen, sulfo, C₁ -C₄ alkyl or C₁ -C₄alkoxy.

As blue dyeing dyes it is preferred to use for the inventive process atleast one dye of formulae ##STR11## especially the dye of formula (16).

As red dyeing dyes it is preferred to use for the inventive process atleast one dye of formulae (20), (21), (22), (23) and (24) ##STR12##wherein R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ and R₂₇ are hydrogen, unsubstituted orsubstituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo,ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted inthe alkyl moiety, and A₃ is a radical of formula ##STR13## wherein R andR' are hydrogen or unsubstituted or substituted C₁ -C₈ alkyl, and Y₃ ishydroxy, C₁ -C₄ alkoxy, chloro, bromo, C₁ -C₄ alkylthio, amino, N-mono-or N,N-di-C₁ -C₄ alkylamino which is unsubstituted or substituted in thealkyl moiety or moieties by hydroxy, sulfo, carboxy or C₁ -C₄ alkoxy,cyclohexylamino, phenylamino or N-C₁ -C₄ alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl nucleus by C₁ -C₄ alkyl, C₁-C₄ alkoxy, carboxy, sulfo and/or halogen, or are morpholino or3-carboxy- or 3-carbamoylpyridin-1-yl, ##STR14## wherein R₂₈, R₂₉, R₃₀and R₃₁ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁-C₈ alkoxy, halogen, carboxy, sulfo, ureido, sulfamoyl or C₂ -C₆alkanoylamino which is unsubstituted or substituted in the alkyl moiety,and A₄ is as defined for A₃ under formula (20), ##STR15## wherein R₃₂,R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ are hydrogen, unsubstituted orsubstituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo,ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted inthe alkyl moiety, and R₃₉ is benzoylamino or benzoylamino which issubstituted in the phenyl ring, or a radical of formula ##STR16## whichmay be further substituted in the phenyl ring, wherein R and R' arehydrogen or unsubstituted or substituted C₁ -C₈ alkyl and Y₄ is asdefined for Y₃ under formula (20), ##STR17## wherein R₄₀, R₄₁, R₄₂, R₄₃,R₄₄, R₄₅, R₄₆ and R₄₇ are hydrogen, unsubstituted or C₁ -C₈ alkyl or C₁-C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylaminowhich is unsubstituted or substituted in the alkyl moiety, and R₄₀ andR₄₆ may additionally be phenylazo or phenylazo which is substituted inthe phenyl ring, and A₅ is as defined for A₃ under formula (20), or is aradical of formula ##STR18## wherein R and R' are hydrogen orunsubstituted or substituted C₁ -C₈ alkyl and Y₅ is as defined for Y₃under formula (20), ##STR19## wherein R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃ andR₅₄ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety, and A₆ is as definedfor A₃ under formula (20).

Halogen substituents R₂₂, R₂₃, R₂₄, R₂₅, R₂₆ and R₂₇ in formula (20),R₂₈, R₂₉, R₃₀ and R₃₁ in formula (21), R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ andR₃₈ in formula (22), R₄₀, R₄₁, R₄₂, R₄₃, R₄₄, R₄₅, R₄₆ and R₄₇ informula (23), and R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃ and R₅₄ in formula (24)are each independently of one another typically fluoro, bromo or,preferably, chloro.

Unsubstituted or substituted C₁ -C₈ alkyl cited above as substitutent ofthe dyes of formulae (20) to (24) as well as suitable value for R and R'is preferably C₁ -C₄ alkyl, typically methyl, ethyl, propyl, isopropyl,butyl, sec-butyl, tert-butyl or isobutyl, as well as the radicalssubstituted by e.g. C₁ -C₄ alkoxy, C₁ -C₄ alkoxycarbonyl, hydroxy,halogen, typically chloro or fluoro, carboxy, cyano, sulfo or sulfato.

R and R' have the previously given meanings and preferred meanings.

Unsubstituted or substituted C₁ -C₈ alkoxy cited above as substituentsof the dyes of formulae (20) to (24) is preferably C₁ -C₄ alkoxy,typically methoxy, ethoxy, propoxy, isopropoxy, butoxy, sec-butoxy,isobutoxy or tert-butoxy, as well as the hydroxy- or carboxy-substitutedradicals.

C₂ -C₆ Alkanoylamino cited above as substituent of the dyes of formulae(20) to (24) is preferably C₂ -C₄ alkanoylamino, typically acetylaminoor propionoylamino. C₂ -C₆ alkanoylamino which is substituted in thealkyl moiety may suitably be hydroxy-substituted.

R₃₉ as benzoylamino or as radical of formula ##STR20## as well as R₄₀and R₄₆ as phenylazo may be unsubstituted or substituted in the phenylring. Typical examples of substituents are halogen, amino, sulfo,carboxy, ureido, C₂ -C₄ alkanoylamino which may be further substitutedin the alkyl moiety by hydroxy, C₁ -C₄ alkyl, C₁ -C₄ alkoxy which may befurther substituted by hydroxy, as well as benzoylamino or phenylaminowhich may be further substituted in the phenyl ring by carboxy, halogen,sulfo, C₁ -C₄ alkyl or C₁ -C₄ alkoxy. Preferred substituents arehalogen, sulfo or C₁ -C₄ alkyl.

Y₃, Y₄ and Y₅ have the same meanings and preferred meanings as givenabove for Y₁ and Y₂.

As red dyeing dyes it is preferred to use for the inventive process atleast one dye of formula ##STR21## especially a dye of formula (25).

It is particularly preferred to use at least one yellow or orange dyeingdye of formula (1) together with at least one blue dyeing dye offormulae (13) to (15) and/or at least one red dyeing dye of formulae(20) to (24). As blue dyeing dyes those of formulae (13) and (15), andas red dyeing dyes those of formulae (21), (23) and (24), meritparticular interest.

In the process of this invention it is especially preferred to use atleast one yellow or orange dyeing dye of formula (1), preferably ayellow or orange dyeing dye of formulae (11) and (12), together with atleast one blue dyeing dye of formulae (16), (17), (18), (19) and (19a)and/or at least one red dyeing dye of formulae (25) to (29), the bluedyeing dye being preferably the dye of formula (16) and the red dyeingdye preferably being the dye of formula (25).

A particularly important embodiment of the process of this inventioncomprises using a yellow or orange dyeing dye of formula (11) togetherwith a blue dyeing dye of formula (16) and/or a red dyeing dye offormula (25).

The process of this invention is particularly suitable for trichromaticdyeing or printing using at least one yellow or orange dyeing dye offormula (1) together with at least one blue dyeing dye and at least onered dyeing dye. With respect to the dyes used for trichromatic dyeing orprinting, the meanings and preferred meanings previously given aboveapply.

By trichromatic dyeing is meant the additive blending of suitably chosenyellow or orange, red and blue dyeing dyes in the concentrationsnecessary for obtaining the desired shade.

The yellow or orange dyeing dyes of formula (1), the blue dyeing dyes offormulae (13) to (15) and the red dyeing dyes of formulae (20) to (24)are known or they can be prepared by methods analogous to those forobtaining known dyes.

With respect to their tinctorial properties, the yellow or orange dyeingdyes of formula (1), the blue dyeing dyes of formulae (13) to (15) andthe red dyeing dyes of formulae (20) to (24) used in the process of thisinvention may be termed direct dyes (C.I. direct dyes).

The yellow or orange dyeing dyes of formula (1), the blue dyeing dyesand the red dyeing dyes used in the inventive process are either in theform of their free sulfonic acid or, preferably, as salts thereof,typically as alkali metal salts, alkaline earth metal salts or ammoniumsalts or as salts of an organic amine. Typical examples are the sodium,potassium, lithium or ammonium salts or the salt of triethanolamine.

For the inventive process, the concentrations in which the yellow ororange dyeing dyes of formula (1), the blue dyeing dyes and the reddyeing dyes are used in the dyebaths or printing pastes vary, dependingon the desired depth of shade. In general, concentrations of 0.01 to 10percent by weight, preferably of 0.1 to 6 percent by weight, based onthe material to be dyed, have been found useful.

Suitable hydroxyl group containing fibre materials, especially textilematerials, which can be dyed or printed by the process of the inventionare typically those made from cellulosic fibres such as cotton, linen orhemp, preferably cotton, as well as regenerated cellulose fibres such asviscose rayon, rayon or viscose staple fibres.

Hydroxyl group containing fibre materials will also be understood asmeaning blends containing such fibre materials. Suitable blends aretypically those containing, in addition to cellulosic fibre materials,natural or synthetic polyamide fibre materials or acrylic or polyesterfibre materials. Exemplary of such blends are wool/cotton,polyamide/cotton, acrylic/cotton or, preferably, polyester/cottonblends.

The textile materials can be in any form of presentation, typically asfilaments, yarn, woven or knitted goods.

The process of the invention is suitable for dyeing by the exhaust orthe pad method as well as for printing by the standard methods employed.

Dyeing by the exhaust method is preferred. Exhaust dyeing is normallycarried out in the temperature range from 60° to 110° C., preferablyfrom 9° to 105° C., in the pH range from 6 to 10, preferably from 7 to9, preferably from an aqueous liquor at a liquor to goods ratio of 1:5to 1:80, most preferably of 1:10 to 1:20.

A particularly preferred embodiment of the inventive process comprisesdyeing in the presence of a salt, conveniently in the presence of analkali metal halide, preferably an alkali metal chloride, or of analkali metal sulfate. A portion of the salt is preferably added at thestart of the dyeing process and then a further portion is added,altogether or in increments, shortly before or after the dyeingtemperature has been reached. The amount of salt added at the start ofthe dyeing process is normally from 5 to 40% of the total amount of saltadded in the course of the dyeing process. The amount of salt addedshortly before or after the dyeing temperature has been reached is thus60 to 95% of the total amount of salt added in the course of the dyeingprocess. The temperature range shortly before dyeing temperature isreached will be understood as meaning the heating up range for attainingthe dyeing temperature, typically the temperature range from 80° to 98°C. It is preferred to add the salt direct when the dyeing temperature isreached. In this embodiment of the inventive process it has been founduseful to add a total amount of salt depending on the total amount ofthe dyes used. Normally the total amount of salt added will increasewith the total amount of the dyes. The amount of salt added is typically6 to 12 g/l up to a total amount of 1% of dye, typically 12 to 20 g/l upto a total amount of 2% of dye, and typically 20 to 40 g/l above a totalamount of 2% of dye. The dye concentrations are here expressed inpercentages by weight, based on the fibre material, and normallycorrespond to the dyes obtained after their synthesis, conveniently bysalting out.

Dyeing by the exhaust method is preferred for this embodiment of theinventive process. It is also possible to dye textile fibre materialsmade from blends, typically from wool/cotton, polyamide/cotton,acrylic/cotton or, preferably polyester/cotton blends by one bathprocesses and in the presence of dyes for the other different type offibre component.

It is thus possible to dye blends of synthetic fibres and cellulosicfibre materials, preferably polyester/cotton blends, in the presence ofa disperse dye for the synthetic fibre component under the dyeingconditions for synthetic fibres. Suitable synthetic fibres arepreferably polyester fibres. If dyeing is carried out in this embodimentof the process in the presence of a salt such as an alkali metal halideor an alkali metal sulfate, then it is preferred to add the total amountof salt at the start of the dyeing process.

The dyes used for the inventive process have good compatibility withother dyes, especially disperse dyes. They have a sufficienthigh-temperature stability and can hence be used for dyeing under thedyeing conditions for polyester fibres, i.e. in the temperature rangefrom about 100° to 150° C., preferably from 120° to 130° C., from anaqueous liquor and in the pH range from about 4 to 7.5, preferably from5 to 7.

It is thus possible to use conventional disperse dyes together with thedyes eligible for the process of this invention in a single step, onebath process for dyeing polyester/cotton blends, in which process leveland fast dyeings are obtained with the respective dye on both fibrecomponents. By using a disperse dye of the same shade as the dye mixtureused for the inventive process, it is also possible to obtain solidshade dyeings.

The dyeing of textile blends, typically blends of polyester andcellulosic fibres, can be greatly simplified in this embodiment of theinventive process. The conventional practice of dyeing each component ofa fibre blend in a separate procedure under different dyeing conditionsis therefore no longer necessary.

The dyes used for the process of this invention are distinguished bylevel colour build-up while having consistency of shade at differentconcentrations and good compatibility with other dyes. The dyeings andprints obtained have good fibre levelness and surface levelness and goodallround fastness properties, especially good fastness to rubbing, wettreatments, wet rubbing, perspiration and light. Where necessary, thewetfastness properties, especially the washfastness, can be furthersubstantially enhanced by an aftertreatment with fixing alkalies.Examples of suitable fixing alkalies are those described in EP-A-250 265and EP-A-438 380.

The invention is illustrated by the following Examples in which partsand percentages are by weight, unless otherwise indicated. Therelationship between parts by weight and parts by volume is the same asthat between the kilogram and the litre.

EXAMPLE 1

12.5 parts of non-mercerised cotton fabric are wetted with one part of anon-ionic wetting agent at 80° C. The pretreated cotton fabric ispinched off and put into a warm dye solution of 40° C. which contains,in deionised water, 0.4% of the yellow dyeing dye of formula ##STR22##0.3% of the red dyeing dye of formula ##STR23## and 0.3% of the bluedyeing dye of formula ##STR24## based on the weight of the cottonfabric, at a liquor ratio of 1:20. The dyebath is kept for 5 minutes ata temperature of 40° C., then 3 g/l of sodium sulfate are added and,after a further 5 minutes, the temperature of the dyebath is raised toboiling temperature at a heating-up rate of 1.5° C./minute. When boilingtemperature is reached, 12 g/l of sodium sulfate are added and thedyebath is kept for 45 minutes at c. 98° C. Then the dyebath is cooledto c. 80°-85° C. at a cooling rate of 1° C./minute and kept for 15minutes at this temperature. The dyed fabric is then removed from thebath, washed twice for 5 minutes with water, pinched off and dried in adrying oven at c. 80°-90° C. The cotton is dyed in a level ochre brownshade of good allround fastness properties. The fastness properties,especially the washfastness, are enhanced by subjecting the dyed cottonfabric to an aftertreatment with a cationic fixing agent.

EXAMPLES 2 to 26

The procedure of Example 1 is repeated, but replacing 0.4% of the yellowdyeing dye of formula (101), 0.3% of the red dyeing dye of formula (102)and 0.3% of the blue dyeing dye of formula (103) with the dyes listed incolumn 2 of the following Table in the given concentrations, and usinginstead of 3 g/l sodium sulfate the amount of sodium sulfate A indicatedin column 3, and instead of 12 g/l of sodium sulfate the amount ofsodium sulfate B indicated in column 4, to give a cotton fabric dyed inthe shade indicated in column 5. The dyes of formulae (104) to (111)specified in column 2 are listed after the Table.

                  TABLE                                                           ______________________________________                                                          Sodium sul-                                                                             Sodium sul-                                       Ex.  Dyes         fate A    fate B  Shade                                     ______________________________________                                         2   0.4% of the dye of                                                                         1.5    g/l  13.5 g/l  olive green                                formula 101)                                                                  0.3% of the dye                                                               formula (104)                                                                 0.3% of the dye of                                                            formula (103)                                                             3   0.4% of the dye of                                                                         1.6    g/l  9.2  g/l  ochre brown                                formula (101)                                                                 0.3% of the dye of                                                            formula (102)                                                                 0.1% of the dye of                                                            formula (105)                                                             4   0.4% of the dye of                                                                         3.2    g/l  9.7  g/l  brown                                      formula (101)                                                                 0.3% of the dye of                                                            formula (102)                                                                 0.2% of the dye of                                                            formula (106)                                                             5   1.0% of the dye of                                                                         3.0    g/l  12,6 g/l  olive green                                formula (101)                                                                 0.5% of the dye of                                                            formula (103)                                                             6   1.0% of the dye of                                                                         3.0    g/l  12.6 g/l  orange                                     formula (101)                                                                 0.5% of the dye of                                                            formula (102)                                                             7   0.4% of the dye of                                                                         2.0    g/l  13.0 g/l  grey olive                                 formula (101)                                                                 0.3% of the dye of                                                            formula (107)                                                                 0.3% of the dye of                                                            formula (103)                                                             8   0.4% of the dye of                                                                         3.2    g/l  7.6  g/l  grey olive                                 formula (101)                                                                 0.3% of the dye of                                                            formula (107)                                                                 0.1% of the dye of                                                            formula (105)                                                             9   0.4% of the dye of                                                                         2.5    g/l  10.4 g/l  brown olive                                of formula (101)                                                              0.3% of the dye of                                                            formula (107)                                                                 0.2% of the dye of                                                            formula (106)                                                            10   1.0% of the dye of                                                                         3.2    g/l  12.4 g/l  orange                                     formula (101)                                                                 0.5% of the dye of                                                            formula (107)                                                            11   0.4% of the dye of                                                                         3.0    g/l  12.0 g/l  grey brown                                 formula (101)                                                                 0.3% of the dye of                                                            formula (108)                                                                 0.3% of the dye of                                                            formula (103)                                                            12   0.4% of the dye of                                                                         2.1    g/l  8.5  g/l  brown                                      formula (101)                                                                 0.3% of the dye of                                                            formula (108)                                                                 0.1% of the dye of                                                            formula (105)                                                            13   0.4% of the dye of                                                                         2.5    g/l  10.4 g/l  brown                                      formula (101)                                                                 0.3% of the dye of                                                            formula (108)                                                                 0.2% of the dye of                                                            formula (106)                                                            14   1.0% of the dye of                                                                         3.2    g/l  12.4 g/l  brown orange                               formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                            15   0.5% of the dye of                                                                         4      g/l  15   g/l  brown orange                               formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                                 0.5% of the dye of                                                            formula (107)                                                            16   0.5% of the dye of                                                                         5      g/l  15   g/l  greenish                                   formula (101)                      grey olive                                 0.5% of the dye of                                                            formula (103)                                                                 0.5% of the dye of                                                            formula (107)                                                            17   0.5% of the dye of                                                                         6      g/l  13   g/l  brown                                      formula (101)                      violet                                     0.5% of the dye of                                                            formula (109)                                                                 0.5% of the dye of                                                            of formula (107)                                                         18   0.5% of the dye of                                                                         7      g/l  11   g/l  orange                                     formula (101)                                                                 0.5% of the dye of                                                            formula (110)                                                                 0.5% of the dye of                                                            formula (107)                                                            19   0.5% of the dye of                                                                         3.5    g/l  14.5 g/l  grey olive                                 formula (101)                                                                 0.5% of the dye of                                                            formula (111)                                                                 0.5% of the dye of                                                            formula (107)                                                            20   0.5% of the dye of                                                                         3      g/l  16   g/l  greenish                                   der Formel (101)                   grey olive                                 0.5% of the dye of                                                            formula (105)                                                                 0.5% of the dye of                                                            formula (107)                                                            21   0.5% of the dye of                                                                         4      g/l  14   g/l  red orange                                 formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                                 0.5% of the dye of                                                            formula (107)                                                            22   0.5% of the dye of                                                                         4      g/l  14.5 g/l  red orange                                 formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                                 0.5% of the dye of                                                            formula (110)                                                            23   0.5% of the dye of                                                                         3.5    g/l  15.5 g/l  grey brown                                 formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                                 0.5% of the dye of                                                            formula (111)                                                            24   0.5% of the dye of                                                                         4.5    g/l  14.5 g/l  anthracite                                 formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                                 0.5% of the dye of                                                            formula (105)                                                            25   0.5% of the dye of                                                                         5      g/l  13   g/l  aubergine                                  formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                                 0.5% of the dye of                                                            formula (109)                                                            26   0.5% of the dye of                                                                         6      g/l  13   g/l  grey brown                                 formula (101)                                                                 0.5% of the dye of                                                            formula (108)                                                                 0.5% of the dye of                                                            formula (103)                                                            ______________________________________                                    

List of dyes of formulae (104) to (111) indicated in the above Table:##STR25##

EXAMPLE 27

250.8 parts of thoroughly wetted polyester/cotton knit goods comprising30 parts of polyester and 70 parts of cotton per 100 parts are put at60° C. into a high-temperature jet dyeing machine. The liquor ratio is1:7. The following auxiliaries are then added to the dyebath:

0.75 g/l of a commercially available lubricant (oxyalkylene-polyestercondensate type),

0.3 g/l of a maleate-based silicone-free penetration accelerator,

1 g/l of a levelling assistant (ammonium salt of an acid-modifiedpolyhydroxy alkylene glycol ether),

2 g/l of monosodium dihydrogen phosphate buffer,

2 g/l of sodium-m-nitrobenzenesulfonate and

10 g/l of sodium sulfate.

The pH is adjusted to 5 with acetic acid. The dye liquor is kept for 5minutes at 60° C. and then a mixture of 0.74 part of the dye of formula(101), 0.45 part of the dye of formula (102), 0.48 part of the dye offormula (103), 0.21 part of a yellow dyeing disperse dye of formula##STR26## 0.19 part of a red dyeing disperse dye of formula ##STR27##and 0.17 part of a blue dyeing disperse dye of formula ##STR28## areadded to the dyebath. The dyebath is then heated to 130° C. at aheating-up rate of 2° C./minute, kept at this temperature for 30 minutesand thereafter cooled to 80° C. at a cooling rate of 1.5° C./minute. Thedyebath is kept for 15 minutes at 80° C., then drained off and the dyedmaterial is washed twice for 5 minutes with warm water of 30° C. Thedyeing is finished by drying in conventional manner or treated with acationic aftertreating agent. Suitable aftertreating agents includethose based on polymerised quaternary diallylammonium compounds,typically the compounds described in EP-A-438 380. The material is dyedin a light olive brown shade of excellent levelness.

What is claimed is:
 1. A process for dyeing or printing a hydroxyl groupcontaining fibre material, which comprises applying a mixture of dyes tothe material, wherein said mixture of dyes is a dichromatic mixture ofdyes comprising at least one yellow or orange dyeing dye and at leastone blue dyeing or at least one red dyeing dye, or said mixture of dyesis a trichromatic mixture of dyes comprising at least one yellow ororange dyeing dye, at least one blue dyeing dye and at least one reddyeing dye, wherein the blue dyeing dye is a blue dyeing sulfonated azodye or a blue dyeing azo copper complex dye, said red dyeing dye is ared dyeing sulfonated azo dye or a red dyeing azo copper complex dye andsaid yellow or orange dyeing dye is a dye of the formula ##STR29##wherein R₁ and R₂ are hydrogen, C₁ -C₈ alkyl, C₁ -C₈ alkoxy, halogen,carboxy, sulfo, ureido, C₂ -C₆ alkanoylamino which is unsubstituted orsubstituted in the alkyl moiety, or unsubstituted or substitutedarylazo, R₃, R₄, R₅, R₆, R₇ and R₈ are hydrogen, C₁ -C₈ alkyl, C₁ -C₈alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety, and A₁ is a radical offormula ##STR30## wherein R and R' are hydrogen or unsubstituted orsubstituted C₁ -C₈ alkyl, Y₁ in the radical of formula (3) and Y₂ in theradical of formula (4) is hydroxy, C₁ -C₄ alkoxy, chloro, bromo, C₁ -C₄alkylthio, amino, N-mono- or N,N-di-C₁ -C₄ alkylamino which isunsubstituted or substituted in the alkyl moiety or moieties by hydroxy,sulfo, carboxy or C₁ -C₄ alkoxy, or cyclohexylamino, phenylamino or N-C₁-C₄ alkyl-N-phenylamino which are unsubstituted or substituted in thephenyl moiety by C₁ -C₄ alkyl, C₁ -C₄ alkoxy, carboxy, sulfo or halogen,or are morpholino or 3-carboxy- or 3-carbamoylpyridin-1-yl, and B₁ is alinking group of the formula ##STR31##
 2. A process according to claim1, wherein R₁, R₂, R₃, R₄, R₅, R₆, R₇ and R₈ are hydrogen, C₁ -C₄ alkyl,C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogen or sulfo.
 3. A processaccording to claim 1, wherein R₁, R₂, R₃ and R₄ are hydrogen or sulfo.4. A process according to claim 1, wherein Y₁ and Y₂ are chloro, amino,N-mono- or N,N-di-C₁ -C₄ alkylamino which is unsubstituted orsubstituted in the alkyl moiety or moieties by hydroxy, or arephenylamino or morpholino.
 5. A process according to claim 1, whereinthe dye of formula (1) is a dye of formula ##STR32## wherein R₉ and R₁₀are hydrogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₂ -C₄ alkanoylamino, halogenor sulfo, and A₂ is a radical of formula ##STR33##
 6. A processaccording to claim 1, wherein the dye of formula (1) is a dye of formula##STR34##
 7. A process according to claim 1, wherein said dye mixturecomprises at least one blue dyeing dye of the formula ##STR35## whereinD₁ is unsubstituted or substituted phenyl or naphthyl, R₁₁, R₁₂, R₁₃ andR₁₄ are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety and R₁₅ is hydrogen,unsubstituted or substituted C₁ -C₈ alkyl, unsubstituted C₂ -C₆ alkanoylor C₂ -C₆ alkanoyl which is substituted in the alkyl moiety, or phenylor benzoyl which are unsubstituted or substituted in the phenyl ring, orof the formula ##STR36## wherein D₂ and D₃ are unsubstituted orsubstituted naphthyl, and R₁₆ and R₁₇ are hydrogen, unsubstituted orsubstituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen, carboxy, sulfo,ureido or C₂ -C₆ alkanoylamino which is unsubstituted or substituted inthe alkyl moiety, or of the formula ##STR37## wherein R₁₈, R₁₉ and R₂₀are hydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety, and R₂₁ isunsubstituted or substituted C₁ -C₈ alkyl or phenyl.
 8. A processaccording to claim 1, wherein said dye mixture comprises at least oneblue dyeing dye selected from the group consisting of ##STR38##
 9. Aprocess according to claim 1, wherein said dye mixture comprises atleast one red dyeing dye of the formula ##STR39## wherein R₂₂, R₂₃, R₂₄,R₂₅, R₂₆ and R₂₇ are hydrogen, unsubstituted or substituted C₁ -C₈ alkylor C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido or C₂ -C₆alkanoylamino which is unsubstituted or substituted in the alkyl moiety,and A₃ is a radical of formula ##STR40## wherein R and R' are hydrogenor unsubstituted or substituted C₁ -C₈ alkyl, and Y₃ is hydroxy, C₁ -C₄alkoxy, chloro, bromo, C₁ -C₄ alkylthio, amino, N-mono- or N,N-di-C₁ -C₄alkylamino which is unsubstituted or substituted in the alkyl moiety ormoieties by hydroxy, sulfo, carboxy or C₁ -C₄ -alkoxy, orcyclohexylamino, phenylamino or N-C₁ -C₄ alkyl-N-phenylamino which areunsubstituted or substituted in the phenyl nucleus by C₁ -C₄ alkyl, C₁-C₄ alkoxy, carboxy, sulfo or halogen, or are morpholino or 3-carboxy-or 3-carbamoylpyridin-1-yl, or of the formula ##STR41## wherein R₂₈,R₂₉, R₃₀ and R₃₁ are hydrogen, unsubstituted or substituted C₁ -C₈ alkylor C₁ -C₈ alkoxy, halogen, carboxy, sulfo, ureido, sulfamoyl or C₂ -C₆alkanoylamino which is unsubstituted or substituted in the alkyl moiety,and A₄ is as defined for A₃ under formula (20), or of the formula##STR42## wherein R₃₂, R₃₃, R₃₄, R₃₅, R₃₆, R₃₇ and R₃₈ are hydrogen,unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen,carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted orsubstituted in the alkyl moiety, and R₃₉ is benzoylamino or benzoylaminowhich is substituted in the phenyl ring, or a radical of formula##STR43## which may be further substituted in the phenyl ring, wherein Rand R' are hydrogen or unsubstituted or substituted C₁ -C₈ alkyl and Y₄is as defined for Y₃ under formula (20), or of the formula ##STR44##wherein R₄₀, R₄₁, R₄₂, R₄₃, R₄₄, R₄₅, R₄₆ and R₄₇ are hydrogen,unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy, halogen,carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which is unsubstituted orsubstituted in the alkyl moiety, and R₄₀ and R₄₆ may additionally bephenylazo or phenylazo which is substituted in the phenyl ring, and A₅is as defined for A₃ under formula (20), or is a radical of formula##STR45## wherein R and R' are hydrogen or unsubstituted or substitutedC₁ -C₈ alkyl and Y₅ is as defined for Y₃ under formula (20), or of theformula ##STR46## wherein R₄₈, R₄₉, R₅₀, R₅₁, R₅₂, R₅₃ and R₅₄ arehydrogen, unsubstituted or substituted C₁ -C₈ alkyl or C₁ -C₈ alkoxy,halogen, carboxy, sulfo, ureido or C₂ -C₆ alkanoylamino which isunsubstituted or substituted in the alkyl moiety, and A₆ is as definedfor A₃ under formula (20).
 10. A process according to claim 1, whereinsaid dye mixture comprises at least one red dyeing dye selected from thegroup consisting of ##STR47##
 11. A process according to claim 10,wherein said dye mixture comprises least one yellow or orange dyeing dyeselected from the group consisting of ##STR48## together with at leastone blue dyeing dye selected from the group consisting of ##STR49## andat least one red dyeing dye selected from the group consisting of##STR50##
 12. A process of claim 1 wherein the mixture of dyes is atrichromatic mixture which comprises at least one yellow or orange dyeof formula (1), at least one blue dyeing dye and at least one red dyeingdye.
 13. A process of claim 4 wherein Y₁ and Y₂ are morpholino orchloro.
 14. A process of claim 11 wherein the dye mixture consists of ayellow dyeing dye of formula (11), a blue dyeing dye of formula (16) anda red dyeing dye of formula (25).
 15. A process of claim 1 wherein anaqueous liquor comprising the dye mixture is applied to the material bythe exhaust method, at a dyeing temperature of from 100° C. to 150° C.,in the presence of a salt, wherein a portion of said salt is added tothe aqueous liquor at the beginning of the process and then a furtherportion is added all at once or in increments shortly before the dyeingtemperature is reached.
 16. A process of claim 15 wherein the materialis a polyester/cotton blend, the temperature is from 120° C. to 130° C.,the pH is from 4 to 7.5, and the aqueous liquor comprises the dyemixture and a disperse dye.
 17. A textile material dyed by a process ofclaim 1.